CA1290105C - Colouring keratinous material - Google Patents
Colouring keratinous materialInfo
- Publication number
- CA1290105C CA1290105C CA000529779A CA529779A CA1290105C CA 1290105 C CA1290105 C CA 1290105C CA 000529779 A CA000529779 A CA 000529779A CA 529779 A CA529779 A CA 529779A CA 1290105 C CA1290105 C CA 1290105C
- Authority
- CA
- Canada
- Prior art keywords
- hair
- polysiloxane
- group
- carbon atoms
- colour
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/892—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a hydroxy group, e.g. dimethiconol
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/10—Preparations for permanently dyeing the hair
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Cosmetics (AREA)
Abstract
Abstract of the Disclosure The specification discloses a process for colouring hair in which certain polysiloxanes including siloxane units having a silicon bonded hydroxy group are employed to provide improved depth of colour or colour retention. Preferably the polysiloxanes are employed as a treatment on hair prior to or after application of colorant.
Description
COLOURING KERATINOUS MATERIAL
The present invention is concerned with colouring keratinous material and is particularly concerned with colouring human hair.
Human hair comprises fibres which have a layer of flat scales pointing outward from root to tip. Although the individual scales are thin, they are long ànd overlap each other forming a continuous, multilayered shield around the fibre. Within this shield lies hair cortex which constitutes the bulk of the hair. Dispersed through-out the cortex are pigment particles called melanin. Theirnumber and distribution pattern determine the hair colour.
Hair is composed almost entirely of keratin i.e.
cystine-containing proteins. It is understood that the ~;
two main protein fractions are low- and high-sulphur 15~ proteins. The low-sulphur fraction consists of proteins of high molecular weight and high degree of molecular organization (~-h lical) whereas the hi~h-sulphur proteins are of low molecular weight and do not exhibit any regular ` secondary structure. Both proteins participate in a composite filament-matrix texture which is the dominant structural element of hair cortex. The filaments are com-~; ~ posed of low-sulphur proteins and ~he surrounding matrix is made up of high-sulphur proteins. The chemical compo-sition of the scales differs from that of ~he fibre and~
scale cells do not apparently contain any low-sulphur proteins. The exposed portion of each scale is heavily cross-linked by cystine and this fact, in conjunction with the multilayered shield effect, makes the scales a formi-dable barrier to penetration by chemicals to the interior of the hair fibre.
: ~
:
~: : .~ :
., ~ ~ .
.
:.
~ 2 ~
It is a practice to modify the colour of human hair by the use of hair colorants containing dyes. These hair colorants may be divided conveniently into those which give "permanent", "semi-permanent" or "temporary" results.
By "permanent" is meant that the result of the colouring process remains fast to the action of shampoos, perspira-tion, sunlight and mechanical abrasion until the hair grows out. By "semi-permanent" is meant that the result of the colouring process remains fast to the action of shampoos, perspiration, sunlight and mechanical abrasion for approximately 6 to lO washings with shampoo. By "temporary" is meant that the result of the colouring process may be removed in from one to three shampooings.
In permanent hair colorants the dyes used tat least until recent years) have been predominantly of the oxida-tion type whereby a water insoluble coloured material is produced inside the hair fibre as a result of oxidation of colourless intermediates which penetrate the cortex. The ;
colour forming reactions are accomplished by primary intermediates, secondary intermediates and oxidants.
Primary intermediates include for example p-phenylene-diamine, p-toluenediamine, p-aminodiphenylamine and o,p-aminophenol, p-amino-~-cresol, toluene 2, 5 diamine, N-pheny~-p-phenylenediamine, pyrogallol, 4,4'-diaminodi-phenylene-diamine, p-methylaminophenol, o-phenylenedi-amine, toluene 3, 4 diamine, p-chloro-o-phenylenediamine, o-chloro-p-phenylenédiamine and 2, 6 diaminopyridine. The secondary intermediates, also known as couplers or modi-fiers, are used in conjunction with the primary interme-diates to produce dyes. Secondary intermediates includefor example m-aminophenol, resorcinol, m-phenylenediamine, hydroquinone, resorcine, toluene 2, 4 diamine, l-naphthol, 4-methoxy-m-phenylene-diamine or ~-naphthol and poly-:
, ~, , - ' :, ~ 5 hydroxyphenols. It is believed that the initial oxidation product of p-phenylenediamine for example is benzoquinone diimine. It may react with p~phenylenedi-amine to form a dye but the diimine reacts much faster with secondary intermediates to form a variety of dyes.
By selection of appropriate in~ermediates, various colours may be achieved. The oxidant (otherwise known as the developer) e.g. hydrogen peroxide, sodium perborate, urea peroxide or sodium percarbonate, is usually mixed with the dye intermediates just before use. In addition to its function in relation to the dye intermediates hydrogen peroxide may exert some influence on the colouring of the hair by bleaching ~he melanin. Autoxida~ive dyes have also been proposed with a view to avoiding addition of separate oxidant.
It is a practice to include in permanent hair colo-rants nitro dyes which dye the hair without oxidation e.g.
nitr~ derivatives of aminophenols and benzenediamines~, for example nitro-p-phenylenediamine, p-nitro-o-phenylene-diaminej 4-nitro--o-phenylenediamine,2-amino-4-nitrophenol, 2-amino-5-nitrophenol, picramic acid, 1,4 diaminoanthra-quinone and picric acid. The nitro dyes and also anthraquinone dyes and azobenzene dyes are also commonly used for semi-permanent hair colorants. For example nitrophenylene diamines and nitroaminophenols provide a ; range of yellow, orange, red and violet colours and amino-anthraquinones provide blue colours. Dyestuffs which may be employed for permanent or semi-permanent hair colorant systems also include for example plant hair dyes, or example those derived from henna, walnut or soybean and metallic hair dyes for example those which employ inso-luble salts of for example iron, copper, lead, manganese, nickel or cadmium~
:~ :
, . . .
' i ' ~ '' ,,' : `
:
o,s It is a practice to include in permanent and semi-permanent hair coloran~ compositions not only water and -the dye or dye intermediates but also surfactants (to enhance wetting, cleansing, spreading and viscosity control) for example ammonium oleate, alkanolamides, fatty alkyl sulphates, thickeners for example carboxy methyl cellulose, materials ~o promote diffusion of the dye into hair and materials for solubilizing the dyes. Conhition-ing agents may a~so be included.
Temporary hair colorants make use of generally higher molecular weight dyes which do not pènetrate the hair structure significantly but rather become deposited on the surface. Dyestuffs which may be employ~d for temporary hair colorant systems include oxidation dyes, azo dyes 9 quinoline dyes, acridine dyes, aæine dyes, oxazine dyes, indigoid dyes, anthraquinone dyes, stilbene dyes and thiazole dyes. Temporary hair colorant systems may al80 employ pigments, for example iron oxides, titanium dioxide or carbon black and may employ a binder, for example methacrylate, acrylate, vinylacetate or vinyl-pyrrolidone polymers:or copolymers to assist in binding the hair colorant to the hair, together with dispersion media for example water, acetone, ionic or non-ionic surface active agents, lower alcohols, polyhydric alcohols, higher alcohols, fatty acids and liquid hydro-carbons with a view to ease of application of the colorant and desired texture of the eoloured hair.
It is a practice in the care of hùman hair to apply so-called conditioner compositions with a ~iew to enhancing desired qualities of the hair for exa~ple ease of combing, detzngling, body, shine, texture, split end mending, prevention of static build up and general manage-ability. It has been proposed ~o include in conditioner compositions various ~ilicone product3, including for .
:: :
:`;
~2 ~
example emulsions of the amino silicone polymer amodimethi-cone. E.P. 95 238 discloses materials intended for use as a conditioner for application to hair after shampooing and comprising preferably inter alia certain siloxanes including siloxane units having certain amine, carboxylic, amido groups or quaternised amino groups. It has been for several years the normal practice to apply conditioner .
compositions, which may include for example one or more silicone polymers, to the hair after the operation of colouring the hair has been compl.eted.
We have now found that an improvement in the depth of colour of keratinous material treated with a hair colorant system and in the number of washings through which the :`
colour is retained by the material may be enhanced when certain hydroxyfunctional silicones are employed in conjunction with the colorant system.
The present invention provides, in one of its aspects, in a method of colouring keratinous material by ~ .
means of a hair:colorant system, the~improvemen~ which ~: 20 comprises the use of a polysiloxane c~mprising:at least one :: siloxane unit having the general formula (i) Ra(HO)SiO(3 a~ ,~
:~ in which each ~ represents a monovaIent hydrocarbon group : 25 having 1 to 12 inclusive carbon atoms, or an alkoxy or alkoxyalkoxy group, in which each alkoxy group has up to 7 carbon atoms and a has the value 1 or 2, any other :
siloxane units of the polysiloxane being o~ the general formula ( ii ) Z cSi ( 4 -c ) in which each Z represents a monovalent hydrocarbon group ~ having 1 to 12 inclusive carbon atoms, or an alkoxy or ::
:: :: : :
.
' .
s alkoxyalkoxy group in which each alkoxy group has up to 7 carbon atoms and c has the value 0, 1, 2 or 3 to enhance the depth of colour and/or prolong retention of colour imparted to the hair by the colorant system.
The invention also provides a method of colouring keratinous material comprising the steps of applying a hair colorant system to the material and applying before, during or after application of the colorant system a polysiloxane comprising at least one siloxane unit having the general formula (i) Ra(HO)SiO(3 a) in which each R represents a monovalent hydrocarbon group having 1 to 12 inclusive carbon atoms, or an alkoxy or alkoxyalkoxy group, in which each alkoxy group has up to 7 carbon atoms and _ has the value 1 or 2, any other siloxane units of the polysiloxane being siloxane units of the general formula ~ii) Zcsio(4-c) in which each Z represents a monovalent hydrocarbon group having 1 to 12 inclusive carbon atoms, or an alkoxy or alkoxyalkoxy group, in which each alkoxy group has up to 7 carbon atoms and c has the value 0, I, 2 or 3.
The polysiloxanes are characterised by the presence of at least one silicon-bonded hydroxyl group. Depending ~`
on the value of a, the siloxane units (i) may be present in the polysiloxane as terminal units or as linking units of the polymer or both and may provide any desired proportion of the total siloxane units in the polymer, provided at least one SiOH group is present. Preferably siloxane units (i) provide rom about 0 f 1 to about 20 percent, more preferably 1 to 5 percent of the total siloxane units.
. , ~ ~, ; . . .. . .
~ 2 ~ 5 However, they may if desired provide 100 percent of the total units in the polysiloxane. Any remaining siloxane units of the polysiloxane are those according to the general formula (ii) In units (i) and (ii) each R and each Z may be, for example, an alkyl group having 1 to 6 carbon atoms for example methyl, propyl or butyl, or an aryl group, for example phenyl, or an unsaturated aliphatic or alicyclic group, for example vinyl or cyclohexenyl, or an alkoxy or alkoxyalkoxy group having less than 7 carbon atoms, for example methoxy, ethoxy, propoxy or methoxyethoxy.
Preferably the R and Z substituents are selected from alkyl or alkoxy groups having from 1 to 4 inclusive carbon atoms and phenyl groups. The value of c may be 0, 1, 2 or 3 and thus the units (ii) may provide terminal, main chain or branching uni~s in the polysiloxane.
The polysiloxane may be linear or branched and may have a consistency ranging ~rom a mobile liquid to a resinous material. Good results have been achieved by use 2a of materials having viscosities in the range 2 x 10-5 to 1 m2/s. The preferred polysiloxanes are the liquid ~,~
hydroxy polydiorganosiloxanes which have two units of formula (i) in which a has the value 2 and R represents a methyl group, and a plurality of units of formula (ii) in which c has the value 2. Conveniently each Z represents a methyl group. Preferred polysiloxanes are according to the average formula HO(R2si.O)nH
where each R represents a methyl group and _ has a value in 30 the range 6ao to 1700. The polysiloxane is preferably applied to the hair or other keratinous material as an aqueous emulsion of fine particle size.
:: :
, :: : :
:~: : : :
. . ~ .
: . ' ' ' ' " ' .
_ 9 _ In a method according to the invention the poly-siloxane may provide the sole polysiloxane employed in t~e method. However, other polysiloxanes may also be present if desired. For example when further Pnhancement of durability of ~he colour on the hair is desired, it is sometimes possible to achieve this by employing, in addition to the poly~iloxane as aforesaid, a polysiloxa~e having silicon-bonded hydroxyl and/or alkoxy groups together with silicon-bonded groups having active amino groups, for example, groups such as _Si(CH2)3NH2 and _SiCH2CH2NH~CH2)3NH2. Such amino-containing polysiloxanes are known and include, for example, amodimethicone.
In a method according to the invention the hair colorant syste~ may be any of those conventionally used for the temp~rary, ~emi-permanent or permanent colouring of hair as referred to above. The hair colorant system may conveniently comprise water based anionic, nonionic or cationic emulsions and may include usual additives as referred to above. Various commercially available hair colorant systems may be employed in a method according to the in~ention, for example those supplied by Elida Gibbs, ~ristol Myers and Clairol under the trademarks "Harmony,' "Glints"and"Clairol"re~pectively.
In a method according to the invention the polysi-loxane may be applied to the keratinous material inadmixture wi~h the colorant system, but it is preferably applied before or after application of the colorant system for example in a shampoo used on the keratinous material before application of the colorant system, or in a conditioner rinse applied to the keratinous material after applic.at~on of the colorant system.
.
`
:, A method for colouring hair according to the inven-tion may be carried out for example by first washing the hair using a conventional shampoo formulation comprising for example about 20% by weight sodium laurylethersulphate, rinsing with water, drying to the towel dry stage as by padding it to a substantially dry condition and thereafter applying the chosen polysiloxane in aqueous emulsion to the hair whilst the hair is in this substantially dry condition. The hair, after about one minute, may be brought again to the towel dry stage and the colorant system applied and left in place for about 15 to 20 minutes. The hair may then be rinsed to remove residual colouring matter and dried by forced hot air treatment.
A method according to the invention may be employed in the colouring of virgin hair, or in the colouring of hair which has become damaged e.g. as a result o~ bleach-ing or of permanent waving, to provide the hair with an enhanced depth of colour. Using the preferred poly-siloxanes one may also achieve a prolonged retention of the imparted colour as compared with other methods.
There now follows a description of examples of the invention. In the examples, the symbol Me represents the methyl group. All proportions mentioned in the examples are by weight unless otherwise specified.
In the examples, various commercially available hair colorant systems were used strictly in accordance with their supplier's instructions to colour switches of virgin hair of European origin, portions of which had been bleached and portions of which remained unbleached, to provide coloured standard samples of bleached and unbleached virgin hair of each colour. Comparative samples of coloured hair were prepared from similar .
~:
- ;, . .
`: ' ' ~z~
switches of virgin and bleached virgin hair using control compositions or polysiloxane compositions as a treatment for thc commercial hair colorant systems. The colour of the coloured bleached and unbleached portions of the samples waq observed and compared with the standard shortly after the colouring operation and, for some samples, after several washes. Except where otherwise specified herein, the various commercially available hair colorant systems used were of the semi-permanent type.
Bleaching of portions of the virgin hair switches was carried out as follows. An end portion of each switch of virg~n hair was dipped for two hours at room tempera-ture in a solution formed by mixing equal parts by volume of solutions A and B. Solution A was a 50% by volume : 15 aqueous solution of hydrogen peroxide. Solution B was a : mixture of 13.5 parts by volume am~onia (sp.gr 0.88) 3 parts by ~ol~me ~mpicol ESB 3 (a sodium lauryl ether ~ s~lphat~) and 83.5 parts by volume water. After two : ~ hours, the hair was removed from the solution, rinsed in running water and then dried using air heated to 70C.:
Control composition 1 was a 0.35~ solids aqueous:
solution of the:quaternary ammonium salt cetalkonium chloride Control composition 2 was a 0.35% solids aqueous solution of a polysiloxane polyoxyalkylene copo-: 25 lymer:according to the average general formula ~: Me3SiO(Me2SiO)x(l~eB'SiO)ySiMe3 where R' represents -c3H5o(c2H4o3n(cH3c2H3o)mH as supplied by Dow Corning Llmi~ed under the trademark "Dow Corning 193"Suractant.
Polysiloxane 1 was an aqueous emulsion oi pH of about 30 7.2 containing 0.35% of a hydroxyl terminated poly-dimethylsiloxane having the average ~ormula HO~Me2SiO)nH in which n has a value of about 1100 100.
.
* Trademark .
.
. . . . .
'; ~ ~: ; . .
. . .
~ ~ . . . . .
.
.
~z~
Polysiloxane 2 was an aqueous emulsion formed from 0.35% of a hydroxyl terminated polydimethylsiloxane of average formula HO(Me2SiO)nH in which n has a value of about 20 water and'~ergitol TM~6j'' isolaureth-6, a nonionic surfactant.
In examples l and 2 the various hair colorant systems, with and without pretreatment using control compositions and polysiloxanes 1 and 2 were employed to colour switches of bleached and unbleached virgin hair as aforesaid in the following way. The samples produced without pretreatment provided the standard samples and those produced with pretreatment provided the compara~ive samples. The hair was shampooed using a 20% active sodium laurylether sulphate water based composition. The hair wa~
rinsed and padded dry to a towel dry condition. The selected coloraat, made up according to the supplier's instructions was applied to bleached and unbleached portions of the treated hair by covering the hair with the colorant for twenty minutes. The hair was rinsed in running water until the water was colourless. The hair was dried in air heated to 70C until the hair became dry. In those cases in which a pretreatment with a control or polysiloxane 1 was employed, after the hair had been padded dry following the initial shampoo and rinse stages, the 2S bleached and unbleached portions of the hair were dipped for one minute in the control composition or the polysiloxane. The hair was removed from the composition and padded dry to a towel dry condition. The selected colorant was then applled to the hair, the hair rinsed and dried as aforesaid. The colour o~ the bleached and un-bleached portions of the sample~ was observed and compared to that of the standards shortly after the hot air drying step.
.
; * Trademark :
; ,~',' , :
: ' - .: ..... : .,. ~ : - -. : . ,. ~ . . :
., .
; . ' ' .,.': ~', '.
.
Example 1 Control compositions 1 and 2 and polysiloxane 1 we~e e~aluated as pretreatments for hair colorant systems using products supplied by Elida Gibbs under the designation 5 " ~armony Auburn "and'~armony Rich Chestnut"using the me~hod described above. Polysiloxan4 2 was evaluated using " Harmony Auburn." By inspection of the sa~lples coloured with"Harmony Rich Chestnut"it was found that the depth of colour of the coloured bleached and unbleached portions of the sample made using control composition 2 was the same as the depth of colour of the corresponding portions of the coloured standard, whereas control compssition 1 gave slightly more depth of colour on the bleached and unbleached portions than the standard. In comparison, ~he samples made using polysiloxane 1 had a greater depth of colour on the bleached and lmbl~ached portions tha~ ~he ` corresponding portions of the coloured sample made using eontrol composition 1.
By inspection of the samples coloured with'~armony 2~ A~urn" it was found tha~ the depth of colour of the coloured bleached and unbleached portions of the samp~es made using control composition 1 and~2 were similar to each other and greater than the depth of colour of corres-ponding portions of the standard. In comparison, the sample made using polysiloxane 1 had a greater depth of colour on its bleached and unbleached portions than the corresponding portions of the sample made using control composition 1. In coniunction with'~armony Aubur~ and in con~unction w~th"Harmony Rich Che~tnut" the coloured bleached and unbleached portions of the samples made using polysiloxane 1 showed better depth of colour as compared with the corresponding portions of the ~tandard. Using polysiloxane 2 and"Harmony Auburn,' some improvement in depth of colour was achieved as compared with the corresponding portions of the standard.
* Trademark A ** ..
. . . ` .
.. .. .. ..... ~, .. .`..... . . .
, .. ~ ,., ~ ., ~ . .. .
. .
., ~ . .
Example 2 Switches of bleached and unbleached virgin hair were coloured with ~armony Auburn and Harmony Rich Chestnut with and without pretreatment using polysiloxane 1 and control compositions, using ~he method described above. The coloured samples were subjected to wash cycles each invol-ving washing the sample in 20% active aqueous solution of sodium lauryl ether sulphate, rinsing with clean water, a second wash in 20% active sodium lauryl ether sulphate, and a second rinse with clean water ~ollowed by drying with air heated to 70C. A~ter each wash cycle each sample was inspected and the colour noted. It was noted that some colour from each sample was washed out. The wash cycles were repeated until the colour on the bleached and unbleached portions of each comparative sample was the same as the colour of the corresponding portion of its washed standard counterpart. The number of wash cycles completed prior to attaining this colour match is shown in the following table:
umber of Washes to Match SamE~e Pretreatment Auburn Rich Chestnut Control 1 2 5 Control 2 3 0 Polysiloxane 1 2 7 These results indicate that hair samples coloured by a method according to the invention retain their colour through more shampooings than hair coloured without pre-treatment using a polysiloxane having units of formula (i~.
. .
~, . :, , . . : , . . ....... .
.. .
- , ' ~ ', :. , .
Example 3 Polysiloxanes l and 2 were evaluated as post-treatment for hair colorant systems using Harmony Auburn using the method employed for Examples 1 and 2 with the exceptlon that no pretreatment was carried out, but a post-treatment was carried out after application of the colorant and after the associated rinsing step.
The coloured hair was padded dry. The post-treatment comprised application to the hair of control composition 1 or a polysiloxane by dipping the coloured hair into the appropriate composition and then drying the hair in air heated to 70C. A good depth of colour, both on bleached portions of the hair and on unbleached portions, was observed on samples in which polysiloxanes 1 or 2 had been used as post-treatment. This depth of colour was better than those of the corresponding standard counterparts.
Example 4 Samples produced as described in Example 3 were ; subjected to wash cycles and inspections as described in Example 2. The number of wash cycles completed prior to the colour on the bleached and unbleached portions of each comparative sample being the same as the colour of the corresponding portion of its washed standard counterpart is shown in the following table:
Sample Posttreatment Number of Washes to Match Polysiloxane 1 4 Polysiloxane 2 , . ~~ - :
. .
The present invention is concerned with colouring keratinous material and is particularly concerned with colouring human hair.
Human hair comprises fibres which have a layer of flat scales pointing outward from root to tip. Although the individual scales are thin, they are long ànd overlap each other forming a continuous, multilayered shield around the fibre. Within this shield lies hair cortex which constitutes the bulk of the hair. Dispersed through-out the cortex are pigment particles called melanin. Theirnumber and distribution pattern determine the hair colour.
Hair is composed almost entirely of keratin i.e.
cystine-containing proteins. It is understood that the ~;
two main protein fractions are low- and high-sulphur 15~ proteins. The low-sulphur fraction consists of proteins of high molecular weight and high degree of molecular organization (~-h lical) whereas the hi~h-sulphur proteins are of low molecular weight and do not exhibit any regular ` secondary structure. Both proteins participate in a composite filament-matrix texture which is the dominant structural element of hair cortex. The filaments are com-~; ~ posed of low-sulphur proteins and ~he surrounding matrix is made up of high-sulphur proteins. The chemical compo-sition of the scales differs from that of ~he fibre and~
scale cells do not apparently contain any low-sulphur proteins. The exposed portion of each scale is heavily cross-linked by cystine and this fact, in conjunction with the multilayered shield effect, makes the scales a formi-dable barrier to penetration by chemicals to the interior of the hair fibre.
: ~
:
~: : .~ :
., ~ ~ .
.
:.
~ 2 ~
It is a practice to modify the colour of human hair by the use of hair colorants containing dyes. These hair colorants may be divided conveniently into those which give "permanent", "semi-permanent" or "temporary" results.
By "permanent" is meant that the result of the colouring process remains fast to the action of shampoos, perspira-tion, sunlight and mechanical abrasion until the hair grows out. By "semi-permanent" is meant that the result of the colouring process remains fast to the action of shampoos, perspiration, sunlight and mechanical abrasion for approximately 6 to lO washings with shampoo. By "temporary" is meant that the result of the colouring process may be removed in from one to three shampooings.
In permanent hair colorants the dyes used tat least until recent years) have been predominantly of the oxida-tion type whereby a water insoluble coloured material is produced inside the hair fibre as a result of oxidation of colourless intermediates which penetrate the cortex. The ;
colour forming reactions are accomplished by primary intermediates, secondary intermediates and oxidants.
Primary intermediates include for example p-phenylene-diamine, p-toluenediamine, p-aminodiphenylamine and o,p-aminophenol, p-amino-~-cresol, toluene 2, 5 diamine, N-pheny~-p-phenylenediamine, pyrogallol, 4,4'-diaminodi-phenylene-diamine, p-methylaminophenol, o-phenylenedi-amine, toluene 3, 4 diamine, p-chloro-o-phenylenediamine, o-chloro-p-phenylenédiamine and 2, 6 diaminopyridine. The secondary intermediates, also known as couplers or modi-fiers, are used in conjunction with the primary interme-diates to produce dyes. Secondary intermediates includefor example m-aminophenol, resorcinol, m-phenylenediamine, hydroquinone, resorcine, toluene 2, 4 diamine, l-naphthol, 4-methoxy-m-phenylene-diamine or ~-naphthol and poly-:
, ~, , - ' :, ~ 5 hydroxyphenols. It is believed that the initial oxidation product of p-phenylenediamine for example is benzoquinone diimine. It may react with p~phenylenedi-amine to form a dye but the diimine reacts much faster with secondary intermediates to form a variety of dyes.
By selection of appropriate in~ermediates, various colours may be achieved. The oxidant (otherwise known as the developer) e.g. hydrogen peroxide, sodium perborate, urea peroxide or sodium percarbonate, is usually mixed with the dye intermediates just before use. In addition to its function in relation to the dye intermediates hydrogen peroxide may exert some influence on the colouring of the hair by bleaching ~he melanin. Autoxida~ive dyes have also been proposed with a view to avoiding addition of separate oxidant.
It is a practice to include in permanent hair colo-rants nitro dyes which dye the hair without oxidation e.g.
nitr~ derivatives of aminophenols and benzenediamines~, for example nitro-p-phenylenediamine, p-nitro-o-phenylene-diaminej 4-nitro--o-phenylenediamine,2-amino-4-nitrophenol, 2-amino-5-nitrophenol, picramic acid, 1,4 diaminoanthra-quinone and picric acid. The nitro dyes and also anthraquinone dyes and azobenzene dyes are also commonly used for semi-permanent hair colorants. For example nitrophenylene diamines and nitroaminophenols provide a ; range of yellow, orange, red and violet colours and amino-anthraquinones provide blue colours. Dyestuffs which may be employed for permanent or semi-permanent hair colorant systems also include for example plant hair dyes, or example those derived from henna, walnut or soybean and metallic hair dyes for example those which employ inso-luble salts of for example iron, copper, lead, manganese, nickel or cadmium~
:~ :
, . . .
' i ' ~ '' ,,' : `
:
o,s It is a practice to include in permanent and semi-permanent hair coloran~ compositions not only water and -the dye or dye intermediates but also surfactants (to enhance wetting, cleansing, spreading and viscosity control) for example ammonium oleate, alkanolamides, fatty alkyl sulphates, thickeners for example carboxy methyl cellulose, materials ~o promote diffusion of the dye into hair and materials for solubilizing the dyes. Conhition-ing agents may a~so be included.
Temporary hair colorants make use of generally higher molecular weight dyes which do not pènetrate the hair structure significantly but rather become deposited on the surface. Dyestuffs which may be employ~d for temporary hair colorant systems include oxidation dyes, azo dyes 9 quinoline dyes, acridine dyes, aæine dyes, oxazine dyes, indigoid dyes, anthraquinone dyes, stilbene dyes and thiazole dyes. Temporary hair colorant systems may al80 employ pigments, for example iron oxides, titanium dioxide or carbon black and may employ a binder, for example methacrylate, acrylate, vinylacetate or vinyl-pyrrolidone polymers:or copolymers to assist in binding the hair colorant to the hair, together with dispersion media for example water, acetone, ionic or non-ionic surface active agents, lower alcohols, polyhydric alcohols, higher alcohols, fatty acids and liquid hydro-carbons with a view to ease of application of the colorant and desired texture of the eoloured hair.
It is a practice in the care of hùman hair to apply so-called conditioner compositions with a ~iew to enhancing desired qualities of the hair for exa~ple ease of combing, detzngling, body, shine, texture, split end mending, prevention of static build up and general manage-ability. It has been proposed ~o include in conditioner compositions various ~ilicone product3, including for .
:: :
:`;
~2 ~
example emulsions of the amino silicone polymer amodimethi-cone. E.P. 95 238 discloses materials intended for use as a conditioner for application to hair after shampooing and comprising preferably inter alia certain siloxanes including siloxane units having certain amine, carboxylic, amido groups or quaternised amino groups. It has been for several years the normal practice to apply conditioner .
compositions, which may include for example one or more silicone polymers, to the hair after the operation of colouring the hair has been compl.eted.
We have now found that an improvement in the depth of colour of keratinous material treated with a hair colorant system and in the number of washings through which the :`
colour is retained by the material may be enhanced when certain hydroxyfunctional silicones are employed in conjunction with the colorant system.
The present invention provides, in one of its aspects, in a method of colouring keratinous material by ~ .
means of a hair:colorant system, the~improvemen~ which ~: 20 comprises the use of a polysiloxane c~mprising:at least one :: siloxane unit having the general formula (i) Ra(HO)SiO(3 a~ ,~
:~ in which each ~ represents a monovaIent hydrocarbon group : 25 having 1 to 12 inclusive carbon atoms, or an alkoxy or alkoxyalkoxy group, in which each alkoxy group has up to 7 carbon atoms and a has the value 1 or 2, any other :
siloxane units of the polysiloxane being o~ the general formula ( ii ) Z cSi ( 4 -c ) in which each Z represents a monovalent hydrocarbon group ~ having 1 to 12 inclusive carbon atoms, or an alkoxy or ::
:: :: : :
.
' .
s alkoxyalkoxy group in which each alkoxy group has up to 7 carbon atoms and c has the value 0, 1, 2 or 3 to enhance the depth of colour and/or prolong retention of colour imparted to the hair by the colorant system.
The invention also provides a method of colouring keratinous material comprising the steps of applying a hair colorant system to the material and applying before, during or after application of the colorant system a polysiloxane comprising at least one siloxane unit having the general formula (i) Ra(HO)SiO(3 a) in which each R represents a monovalent hydrocarbon group having 1 to 12 inclusive carbon atoms, or an alkoxy or alkoxyalkoxy group, in which each alkoxy group has up to 7 carbon atoms and _ has the value 1 or 2, any other siloxane units of the polysiloxane being siloxane units of the general formula ~ii) Zcsio(4-c) in which each Z represents a monovalent hydrocarbon group having 1 to 12 inclusive carbon atoms, or an alkoxy or alkoxyalkoxy group, in which each alkoxy group has up to 7 carbon atoms and c has the value 0, I, 2 or 3.
The polysiloxanes are characterised by the presence of at least one silicon-bonded hydroxyl group. Depending ~`
on the value of a, the siloxane units (i) may be present in the polysiloxane as terminal units or as linking units of the polymer or both and may provide any desired proportion of the total siloxane units in the polymer, provided at least one SiOH group is present. Preferably siloxane units (i) provide rom about 0 f 1 to about 20 percent, more preferably 1 to 5 percent of the total siloxane units.
. , ~ ~, ; . . .. . .
~ 2 ~ 5 However, they may if desired provide 100 percent of the total units in the polysiloxane. Any remaining siloxane units of the polysiloxane are those according to the general formula (ii) In units (i) and (ii) each R and each Z may be, for example, an alkyl group having 1 to 6 carbon atoms for example methyl, propyl or butyl, or an aryl group, for example phenyl, or an unsaturated aliphatic or alicyclic group, for example vinyl or cyclohexenyl, or an alkoxy or alkoxyalkoxy group having less than 7 carbon atoms, for example methoxy, ethoxy, propoxy or methoxyethoxy.
Preferably the R and Z substituents are selected from alkyl or alkoxy groups having from 1 to 4 inclusive carbon atoms and phenyl groups. The value of c may be 0, 1, 2 or 3 and thus the units (ii) may provide terminal, main chain or branching uni~s in the polysiloxane.
The polysiloxane may be linear or branched and may have a consistency ranging ~rom a mobile liquid to a resinous material. Good results have been achieved by use 2a of materials having viscosities in the range 2 x 10-5 to 1 m2/s. The preferred polysiloxanes are the liquid ~,~
hydroxy polydiorganosiloxanes which have two units of formula (i) in which a has the value 2 and R represents a methyl group, and a plurality of units of formula (ii) in which c has the value 2. Conveniently each Z represents a methyl group. Preferred polysiloxanes are according to the average formula HO(R2si.O)nH
where each R represents a methyl group and _ has a value in 30 the range 6ao to 1700. The polysiloxane is preferably applied to the hair or other keratinous material as an aqueous emulsion of fine particle size.
:: :
, :: : :
:~: : : :
. . ~ .
: . ' ' ' ' " ' .
_ 9 _ In a method according to the invention the poly-siloxane may provide the sole polysiloxane employed in t~e method. However, other polysiloxanes may also be present if desired. For example when further Pnhancement of durability of ~he colour on the hair is desired, it is sometimes possible to achieve this by employing, in addition to the poly~iloxane as aforesaid, a polysiloxa~e having silicon-bonded hydroxyl and/or alkoxy groups together with silicon-bonded groups having active amino groups, for example, groups such as _Si(CH2)3NH2 and _SiCH2CH2NH~CH2)3NH2. Such amino-containing polysiloxanes are known and include, for example, amodimethicone.
In a method according to the invention the hair colorant syste~ may be any of those conventionally used for the temp~rary, ~emi-permanent or permanent colouring of hair as referred to above. The hair colorant system may conveniently comprise water based anionic, nonionic or cationic emulsions and may include usual additives as referred to above. Various commercially available hair colorant systems may be employed in a method according to the in~ention, for example those supplied by Elida Gibbs, ~ristol Myers and Clairol under the trademarks "Harmony,' "Glints"and"Clairol"re~pectively.
In a method according to the invention the polysi-loxane may be applied to the keratinous material inadmixture wi~h the colorant system, but it is preferably applied before or after application of the colorant system for example in a shampoo used on the keratinous material before application of the colorant system, or in a conditioner rinse applied to the keratinous material after applic.at~on of the colorant system.
.
`
:, A method for colouring hair according to the inven-tion may be carried out for example by first washing the hair using a conventional shampoo formulation comprising for example about 20% by weight sodium laurylethersulphate, rinsing with water, drying to the towel dry stage as by padding it to a substantially dry condition and thereafter applying the chosen polysiloxane in aqueous emulsion to the hair whilst the hair is in this substantially dry condition. The hair, after about one minute, may be brought again to the towel dry stage and the colorant system applied and left in place for about 15 to 20 minutes. The hair may then be rinsed to remove residual colouring matter and dried by forced hot air treatment.
A method according to the invention may be employed in the colouring of virgin hair, or in the colouring of hair which has become damaged e.g. as a result o~ bleach-ing or of permanent waving, to provide the hair with an enhanced depth of colour. Using the preferred poly-siloxanes one may also achieve a prolonged retention of the imparted colour as compared with other methods.
There now follows a description of examples of the invention. In the examples, the symbol Me represents the methyl group. All proportions mentioned in the examples are by weight unless otherwise specified.
In the examples, various commercially available hair colorant systems were used strictly in accordance with their supplier's instructions to colour switches of virgin hair of European origin, portions of which had been bleached and portions of which remained unbleached, to provide coloured standard samples of bleached and unbleached virgin hair of each colour. Comparative samples of coloured hair were prepared from similar .
~:
- ;, . .
`: ' ' ~z~
switches of virgin and bleached virgin hair using control compositions or polysiloxane compositions as a treatment for thc commercial hair colorant systems. The colour of the coloured bleached and unbleached portions of the samples waq observed and compared with the standard shortly after the colouring operation and, for some samples, after several washes. Except where otherwise specified herein, the various commercially available hair colorant systems used were of the semi-permanent type.
Bleaching of portions of the virgin hair switches was carried out as follows. An end portion of each switch of virg~n hair was dipped for two hours at room tempera-ture in a solution formed by mixing equal parts by volume of solutions A and B. Solution A was a 50% by volume : 15 aqueous solution of hydrogen peroxide. Solution B was a : mixture of 13.5 parts by volume am~onia (sp.gr 0.88) 3 parts by ~ol~me ~mpicol ESB 3 (a sodium lauryl ether ~ s~lphat~) and 83.5 parts by volume water. After two : ~ hours, the hair was removed from the solution, rinsed in running water and then dried using air heated to 70C.:
Control composition 1 was a 0.35~ solids aqueous:
solution of the:quaternary ammonium salt cetalkonium chloride Control composition 2 was a 0.35% solids aqueous solution of a polysiloxane polyoxyalkylene copo-: 25 lymer:according to the average general formula ~: Me3SiO(Me2SiO)x(l~eB'SiO)ySiMe3 where R' represents -c3H5o(c2H4o3n(cH3c2H3o)mH as supplied by Dow Corning Llmi~ed under the trademark "Dow Corning 193"Suractant.
Polysiloxane 1 was an aqueous emulsion oi pH of about 30 7.2 containing 0.35% of a hydroxyl terminated poly-dimethylsiloxane having the average ~ormula HO~Me2SiO)nH in which n has a value of about 1100 100.
.
* Trademark .
.
. . . . .
'; ~ ~: ; . .
. . .
~ ~ . . . . .
.
.
~z~
Polysiloxane 2 was an aqueous emulsion formed from 0.35% of a hydroxyl terminated polydimethylsiloxane of average formula HO(Me2SiO)nH in which n has a value of about 20 water and'~ergitol TM~6j'' isolaureth-6, a nonionic surfactant.
In examples l and 2 the various hair colorant systems, with and without pretreatment using control compositions and polysiloxanes 1 and 2 were employed to colour switches of bleached and unbleached virgin hair as aforesaid in the following way. The samples produced without pretreatment provided the standard samples and those produced with pretreatment provided the compara~ive samples. The hair was shampooed using a 20% active sodium laurylether sulphate water based composition. The hair wa~
rinsed and padded dry to a towel dry condition. The selected coloraat, made up according to the supplier's instructions was applied to bleached and unbleached portions of the treated hair by covering the hair with the colorant for twenty minutes. The hair was rinsed in running water until the water was colourless. The hair was dried in air heated to 70C until the hair became dry. In those cases in which a pretreatment with a control or polysiloxane 1 was employed, after the hair had been padded dry following the initial shampoo and rinse stages, the 2S bleached and unbleached portions of the hair were dipped for one minute in the control composition or the polysiloxane. The hair was removed from the composition and padded dry to a towel dry condition. The selected colorant was then applled to the hair, the hair rinsed and dried as aforesaid. The colour o~ the bleached and un-bleached portions of the sample~ was observed and compared to that of the standards shortly after the hot air drying step.
.
; * Trademark :
; ,~',' , :
: ' - .: ..... : .,. ~ : - -. : . ,. ~ . . :
., .
; . ' ' .,.': ~', '.
.
Example 1 Control compositions 1 and 2 and polysiloxane 1 we~e e~aluated as pretreatments for hair colorant systems using products supplied by Elida Gibbs under the designation 5 " ~armony Auburn "and'~armony Rich Chestnut"using the me~hod described above. Polysiloxan4 2 was evaluated using " Harmony Auburn." By inspection of the sa~lples coloured with"Harmony Rich Chestnut"it was found that the depth of colour of the coloured bleached and unbleached portions of the sample made using control composition 2 was the same as the depth of colour of the corresponding portions of the coloured standard, whereas control compssition 1 gave slightly more depth of colour on the bleached and unbleached portions than the standard. In comparison, ~he samples made using polysiloxane 1 had a greater depth of colour on the bleached and lmbl~ached portions tha~ ~he ` corresponding portions of the coloured sample made using eontrol composition 1.
By inspection of the samples coloured with'~armony 2~ A~urn" it was found tha~ the depth of colour of the coloured bleached and unbleached portions of the samp~es made using control composition 1 and~2 were similar to each other and greater than the depth of colour of corres-ponding portions of the standard. In comparison, the sample made using polysiloxane 1 had a greater depth of colour on its bleached and unbleached portions than the corresponding portions of the sample made using control composition 1. In coniunction with'~armony Aubur~ and in con~unction w~th"Harmony Rich Che~tnut" the coloured bleached and unbleached portions of the samples made using polysiloxane 1 showed better depth of colour as compared with the corresponding portions of the ~tandard. Using polysiloxane 2 and"Harmony Auburn,' some improvement in depth of colour was achieved as compared with the corresponding portions of the standard.
* Trademark A ** ..
. . . ` .
.. .. .. ..... ~, .. .`..... . . .
, .. ~ ,., ~ ., ~ . .. .
. .
., ~ . .
Example 2 Switches of bleached and unbleached virgin hair were coloured with ~armony Auburn and Harmony Rich Chestnut with and without pretreatment using polysiloxane 1 and control compositions, using ~he method described above. The coloured samples were subjected to wash cycles each invol-ving washing the sample in 20% active aqueous solution of sodium lauryl ether sulphate, rinsing with clean water, a second wash in 20% active sodium lauryl ether sulphate, and a second rinse with clean water ~ollowed by drying with air heated to 70C. A~ter each wash cycle each sample was inspected and the colour noted. It was noted that some colour from each sample was washed out. The wash cycles were repeated until the colour on the bleached and unbleached portions of each comparative sample was the same as the colour of the corresponding portion of its washed standard counterpart. The number of wash cycles completed prior to attaining this colour match is shown in the following table:
umber of Washes to Match SamE~e Pretreatment Auburn Rich Chestnut Control 1 2 5 Control 2 3 0 Polysiloxane 1 2 7 These results indicate that hair samples coloured by a method according to the invention retain their colour through more shampooings than hair coloured without pre-treatment using a polysiloxane having units of formula (i~.
. .
~, . :, , . . : , . . ....... .
.. .
- , ' ~ ', :. , .
Example 3 Polysiloxanes l and 2 were evaluated as post-treatment for hair colorant systems using Harmony Auburn using the method employed for Examples 1 and 2 with the exceptlon that no pretreatment was carried out, but a post-treatment was carried out after application of the colorant and after the associated rinsing step.
The coloured hair was padded dry. The post-treatment comprised application to the hair of control composition 1 or a polysiloxane by dipping the coloured hair into the appropriate composition and then drying the hair in air heated to 70C. A good depth of colour, both on bleached portions of the hair and on unbleached portions, was observed on samples in which polysiloxanes 1 or 2 had been used as post-treatment. This depth of colour was better than those of the corresponding standard counterparts.
Example 4 Samples produced as described in Example 3 were ; subjected to wash cycles and inspections as described in Example 2. The number of wash cycles completed prior to the colour on the bleached and unbleached portions of each comparative sample being the same as the colour of the corresponding portion of its washed standard counterpart is shown in the following table:
Sample Posttreatment Number of Washes to Match Polysiloxane 1 4 Polysiloxane 2 , . ~~ - :
. .
Claims (8)
1. In a method of colouring keratinous material by means of a hair colorant system, the improvement which comprises the use of a polysiloxane comprising at least one siloxane unit having the general formula (i) in which each R represents a monovalent hydrocarbon group having 1 to 12 inclusive carbon atoms, or an alkoxy or alkoxyalkoxy group, in which each alkoxy group has up to 7 carbon atoms and a has the value 1 or 2, any other siloxane units of the poly-siloxane being of the general formula (ii) in which each Z represents a monovalent hydrocarbon group having 1 to 12 inclusive carbon atoms, or an alkoxy group or alkoxyalkoxy group in which each alkoxy group has up to 7 carbon atoms and c has the value 0, 1, 2 or 3 to enhance the depth of colour and/or prolong retention of colour imparted to the hair by the colorant system.
2. A method according to Claim 1 wherein the polysiloxane is a substantially linear material according to the average formula HO(R2SiO)nH
in which R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group and n has a value in the range 600 to 1700.
in which R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group and n has a value in the range 600 to 1700.
3. A method according to Claim 2 wherein n has a value of about 1100 ? 100.
4. A method according to Claim 1 wherein the keratinous material is human hair, the hair is padded to a substantially dry condition, the colorant system applied to the hair whilst in this substantially dry condition and the polysiloxane is applied to the hair in the form of an aqueous emulsion before or after application of the colorant system to the hair.
5. A method of colouring keratinous material comprising the steps of applying a hair colorant system to the material and applying before, during or after application of the colorant system a polysiloxane comprising at least one siloxane unit having the general formula (i) in which each R represents a monovalent hydrocarbon group having 1 to 12 inclusive carbon atoms, or an alkoxy or alkoxyalkoxy group, in which each alkoxy group has up to 7 carbon atoms and a has the value 1 or 2, any other siloxane units of the polysiloxane being siloxane units of the general formula (ii) in which each Z represents a monovalent hydrocarbon group having 1 to 12 inclusive carbon atoms, or an alkoxy or alkoxyalkoxy:
group in which each alkoxy group has up to 7 carbon atoms and c has the value 0, 1, 2 or 3.
group in which each alkoxy group has up to 7 carbon atoms and c has the value 0, 1, 2 or 3.
6. A method according to Claim 5 wherein the polysiloxane is a substantially linear material according to the average formula HO(R2SiO)nH
in which R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group and n has a value in the range 600 to 1700.
in which R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group and n has a value in the range 600 to 1700.
7. A method according to Claim 6 wherein n has a value of about 1100 ? 100.
8. A method according to Claim 5 wherein the keratinous material is human hair, the hair is padded to a substantially dry condition, the colorant system applied to the dry condition, the colorant system applied to the hair whilst in this substantially dry condition and the polysiloxane is applied to the hair in the form of an aqueous emulsion before or after application of the colorant system to the hair.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08604705A GB2186889A (en) | 1986-02-26 | 1986-02-26 | Colouring keratinous material |
| GB8604705 | 1986-02-26 | ||
| GB8700620A GB2186890B (en) | 1986-02-26 | 1987-01-12 | Colouring keratinous material |
| GB8700620 | 1987-01-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1290105C true CA1290105C (en) | 1991-10-08 |
Family
ID=26290405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000529779A Expired - Lifetime CA1290105C (en) | 1986-02-26 | 1987-02-16 | Colouring keratinous material |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4898595A (en) |
| CA (1) | CA1290105C (en) |
| DE (1) | DE3706053A1 (en) |
| FR (1) | FR2594688B1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE223693T1 (en) * | 1996-01-05 | 2002-09-15 | Schwarzkopf Gmbh Hans | HAIR DYE AND HAIR DYE MUSH FOR DYEING HUMAN HAIR |
| FR2783416B1 (en) * | 1998-08-26 | 2002-05-03 | Oreal | DYE COMPOSITION FOR KERATINIC FIBERS WITH CATIONIC DIRECT DYE AND SILICONE |
| US8002849B2 (en) | 2007-12-19 | 2011-08-23 | L'oreal S.A. | Composition kit, and method for coloring the hair utilizing saccharide-siloxane copolymers |
| US10987284B2 (en) | 2014-07-14 | 2021-04-27 | Michael V. Greene | Volume boosting molding hair coloring creme formulation |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3964500A (en) * | 1973-12-26 | 1976-06-22 | Lever Brothers Company | Lusterizing shampoo containing a polysiloxane and a hair-bodying agent |
| FR2443476A1 (en) * | 1978-12-05 | 1980-07-04 | Oreal | NOVEL SURFACTANT POLYSILOXANES, PROCESS FOR PREPARING SAME AND COMPOSITIONS CONTAINING THE SAME |
| DE3038984A1 (en) * | 1980-10-15 | 1982-05-27 | Bayer Ag, 5090 Leverkusen | METHOD FOR CONTINUOUS COLORING AND SIMULTANEOUS EQUIPMENT OF TEXTILE MATERIALS |
| JPS57130910A (en) * | 1981-02-05 | 1982-08-13 | Kao Corp | Hair treatment agent |
| JPS57192310A (en) * | 1981-05-20 | 1982-11-26 | Kao Corp | Hair dyeing agent composition |
| US4563347A (en) * | 1982-05-20 | 1986-01-07 | Dow Corning Corporation | Compositions used to condition hair |
| LU84463A1 (en) * | 1982-11-10 | 1984-06-13 | Oreal | POLYQUATERNARY POLYSILOXANE POLYMERS |
| US4487883A (en) * | 1982-12-27 | 1984-12-11 | Dow Corning Corporation | One-part moisture cured aminosiloxanes |
| JPS59190910A (en) * | 1983-04-11 | 1984-10-29 | Kao Corp | Hair dye composition |
| LU84894A1 (en) * | 1983-07-01 | 1985-04-17 | Oreal | HAIR COMPOSITION AND METHOD FOR TREATING HAIR |
| LU85303A1 (en) * | 1984-04-13 | 1985-11-27 | Oreal | HAIR COMPOSITION AND METHOD FOR TREATING HAIR |
| LU85549A1 (en) * | 1984-09-21 | 1986-04-03 | Oreal | COSMETIC COMPOSITIONS BASED ON CATIONIC SILICONE AND XANTHANE GUM |
| GB2173515B (en) * | 1985-04-12 | 1989-01-18 | Beecham Group Plc | Hair dye composition |
-
1987
- 1987-02-16 CA CA000529779A patent/CA1290105C/en not_active Expired - Lifetime
- 1987-02-17 US US07/015,185 patent/US4898595A/en not_active Expired - Fee Related
- 1987-02-23 FR FR878702295A patent/FR2594688B1/en not_active Expired - Lifetime
- 1987-02-25 DE DE19873706053 patent/DE3706053A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| DE3706053A1 (en) | 1987-08-27 |
| FR2594688B1 (en) | 1992-02-07 |
| US4898595A (en) | 1990-02-06 |
| FR2594688A1 (en) | 1987-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| GB2186890A (en) | Colouring keratinous material with the aid of a polysiloxane containing an S:-OH moiety | |
| EP3391873A1 (en) | Method and kit for processing hair | |
| CA2482484C (en) | Durable hair treatment composition | |
| WO2003090508A2 (en) | Durable fiber treatment composition | |
| EP3006017B1 (en) | Hair cosmetic | |
| US20030211064A1 (en) | Fiber treatment blend | |
| US20040003473A1 (en) | Silicones | |
| CA1290105C (en) | Colouring keratinous material | |
| JP2001139429A (en) | Hair cosmetic | |
| EP1466582B1 (en) | Hair treatment agent comprising a silylated peptide-silane copolymer | |
| US20030215411A1 (en) | Fiber treatment composition | |
| JP7270243B2 (en) | Fiber modifier and fiber treatment method | |
| WO2007021604A2 (en) | A fiber and hair fiber conditioning treatment composition | |
| JP2004315370A (en) | Hair cosmetic | |
| AU2003234147B2 (en) | Durable fiber treatment composition | |
| CN117794510A (en) | Cosmetic composition | |
| CN111467253A (en) | Hair care cosmetic and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |